The effect of electrical poling on microstructure and performance of a typical ion exchange membrane was studied. Polyvinyl chloride‐based cation exchange membranes containing ZnO nanoparticle were prepared via phase inversion method and then exposed to intense electric fields with different conditions. Potential, transport number, permselectivity, and flux of treated membranes were examined. Results exhibit an acceptable improvement for treated membranes' properties. The electrical resistance of membranes declined sharply by 30% with voltage increasing. Two‐phase model showed the heterogeneity of poled membranes enhanced under poling conditions. The results can be considered for modification of piezoelectric membranes in many cases.